Bis-(phenoxyphenyl) carbonates

ABSTRACT

Detergents containing as an anti-bacterial additive, a bis(phenoxyphenyl) carbonate which is unsubstituted or substituted in one or several of its benzene rings by halogen, lower alkyl or trifluoromethyl.

United States Patent [191 Traber et al.

[ 1 Feb. 6, 1973 [54] BIS-(PHENOXYPHENYL) CARBONATES [75] Inventors: Walter Traber, Riehen; Anton G.

Weiss, Basel, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

{52] US. Cl. ..252/l06, 252/107, 424/301 [51] Int. Cl. ..C11d 3/48 [58] Field of Search ..252/106, 107; 424/301;

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 657,564 2/1963 Canada OTHER PUBLICATIONS Chemical Abstracts, 64(2) 20100, 11, Jan. 17, 1966.

Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis Attorney-Karl F. Jorda et al.

[57] ABSTRACT Detergents containing as an anti-bacterial additive, a bis-(phenoxyphenyl) carbonate which is unsubstituted or substituted in one or several of its benzene rings by halogen, lower alkyl or trifluoromethyl.

12 Claims, No Drawings BIS-(PHENOXYPI-IENYL) CARBONATES CROSS-REFERENCE TO RELATED APPLICATION This is a division of application Ser. No. 747,792, filed July 26, 1968, now US. Pat. No. 3,592,837.

DETAILED DISCLOSURE The present invention concerns new bis-(phenoxyphenyl) carbonates, processes for the production thereof, the use of these esters as active substances for the disinfection of laundered goods and in antibacterial agents and preparations for the combatting of bacteria, as well as the material treated with these carbonic acid esters.

Halogenated 2-hydroxy-diphenyl ethers, having antibacterial properties, are described in British Pat. No. 1,024,022 and esters of halogenated 2-hydroxy-diphenyl ethers with aliphatic dicarboxylic acids also having antibacterial properties are disclosed in Belgian Pat. No. 659,636. These types of compounds, however, are only insufficiently suitable for the disinfection and protection of laundered goods since their bactericidal activity is completely lost when used in washing liquors containing chlorine.

The new bis-(phenoxyphenyl) carbonates correspond to the general formula I:

wherein R R R and R independently of each other each represent hydrogen or a halogen atom of an atomic number of at most 35, and the benzene rings B and B independently of each other are each unsubstituted or are monoto trisubstituted by halogen of an atomic number of at most 35 or by lower alkyl, or monoor disubstituted by the trifluoromethyl group. The carbonic acid esters of general formula I are particularly suitable for the disinfection and protection of 50 spec., Salmonella pullorum, Salmonella typhi, Salmonella paratyphi A and B, Salmonella typhi murium, Salmonella enteritidis, Shigella dysenteriae, Shigella flexneri, Brucella abortus, Proteus mirabilis, Achromobacter spec., Serratia marcescens, Pasteurella pseudotuberculosis. In addition, they have low toxicity to warm blooded animals and have no irritant action at all on the skin and mucous membranes. Because of these good properties, the new esters can be used for the most various purposes, e.g., for the protection of organic materials and useful objects, particularly as bactericidal additives to cleansing materials of all types such as soaps and de' tergents.

Moreover, the new esters can serve as active substances in pharmaceutical preparations, both for internal and external use.

The bis-(phenoxyphenyl) carbonates of the general formula I where R,, R A and B are respectively the same as R,', R,', A and B are obtained according to the invention either by reacting two equivalents of a hydroxydiphenyl ether ofgeneral formula II (El (III) 40' in which formulas R B,', R and R have m;

meanings given in formula I and the benzene rings B and B have the definitions given above, the reactions preferably being performed in the presence of an acid binding agent.

The hydroxy-diphenyl ethers of general formula II are known starting materials or they can be obtained by the process according to British Pat. No. 1,024,022.

j Chlorocarbonates of the general formula Ill also belong to a known class of compounds which can be produced in the known way by reaction of a hydroxy-diphenyl ether of general formula II with phosgene.

For the production of the new carbonic acid esters of the general formula I, the following hydroxydiphenyl ethers of the general formula II can be used:

Staphylococcus lactis, also Bacillus mesentericus, Bacillus pumilus, Bacillus subtilis, Cali forms, Corynebacterium diphtheriae, Chlostridium botulium, Chlostridium butyricum, Clostridium welchii, Clostridium tetani,

Klebsiella pneumoniae, Alcaligenes faecalis, Sarcina 3, 4'-dichloro-2-hydroxy-diphenyl ether, 3, 4', 4'trichloro-2-hydroxy-diphenyl ether, 2, 4-dichloro-2-hydroxy-diphenyl ether, 2, 4'-dibromo-4-chloro-2-hydroxy-diphenyl ether, 4-chloro-2-hydroxy-diphenyl ether, 4,4'-dichloro-2-hydroxy-dipheny! ether, 4-chloro.-4'-bromo-2-hydroxy-diphenyl ether, 4-methyl-4-chloro-2-hydroxy-diphenyl ether, 4,4'-dichloro-5-bromo-2-hydroxy-diphenyl ether, 4,2',4'-trichloro-5-bromo-2-hydroxy-diphenyl ether, 4,2, 4'-trichloro-2-hydroxy-diphenyl ether,

- 4-bromo-4'-chloro-2-hydroxy-diphcnyl ether,

are substituted by at least one and at most three l halogen atoms or by one or two halogen atoms and/or a lower alkyl or trifluoromethyl radical.

1n the process according to the invention, organic bases such as tertiary amines, e.g., pyridine, triethylamine, and inorganic bases such as the hydroxides and carbonates of alkali and alkaline earth metals are used as acid binding agents. Halogenated hydrocarbons, amides, ethers and ether-type compounds are used as solvents or diluents in the process mentioned.

The following examples describe the production of some bis-(phenoxyphenyl) carbonates of the general formula 1. The temperatures are given on degrees Centigrade and parts are to be understood as parts by weight and are related to parts by volume as grams to milliliters.

EXAMPLE 1 144.7 Parts of 4,2,4-trichloro-2-hydroxy-diphenyl ether and 39.5 parts of pyridine are dissolved in 600 parts by volume of methylene chloride. 25 Parts of phosgene are introduced into the clear solution at 1020, during which time white crystals precipitate.

standing. Recrystallized from isopropyl ether, the diester melts at 128-130.

EXAMPLE 2 a. 210 parts of phosgene are separated at 5 to into a solution of 435 parts of 4,2,4'-trichloro-2- hydroxy-diphenyl ether in 900 parts by volume of dry toluene. At 0 to 5", a solution of 166 parts of triethylamine in 300 parts by volume of dry toluene is then added dropwise. The reaction mixture is stirred for 4 hours at room temperature, and the excess phosgene is then removed by sparging dry nitrogen into the mixture. The precipitated amine hydrochloride is filtered off and the filtrate evaporated in vacuo. The residue is vacuum-distilled and 2-(2',4'- dichlorophenoxy)-5-chlorophenyl chlorocarbonate is obtained, B.P. %-l62/ 0.05 Torr.

b. A solution of 148 parts of 2-(2,4- dichlorophenoxy)-5-chlorophenyl chlorocarbonate in 500 parts by volume of methylene chloride is added dropwise to a solution of l 19 parts of 4,2,4-trichloro- Z-hydroxy-diphenyl ether and 32.4 parts of pyridine in 500 parts by volume of methylene chloride at 0 to 5. The reaction mixture is stirred at room temperature for two hours, filtered and the filtrate washed with water and dried with magnesium sulfate. After evaporating the solvent, the 0,0-bis[2-(2,4-dichlorophenoxy)-5- chlorophenyl] carbonate is obtained. M P. 128130 after recrystallization from isopropyl ether.

' "I '7 EXAMPLE 3 A solution of 176 parts of 2-(2,4-dichlorophenoxy)-5-chlorophcnyl chlorocarbonate (cf. Example 2a) in 500 parts by volume of methylene chloride is added dropwise to a solution of 127 parts of 4,4'-dichloro-2- 0 hydroxy-diphenyl ether and 43 parts of pyridine in 500 parts by volume of methylene chloride at 0 to 5. The reaction mixture is stirred at room temperature for 2 hours, filtered, washed with water and dried with magnesium sulfate. After evaporating the solvent, the 0-[ 2- (2',4'5-chlorophenyl[-0'-[2-(4'- chlorophenoxy)-5-chlorophenyl] carbonate is obtained as an oil. The oily product is purified by means of high vacuum distillation. B.P. 260-265/ 0.05 Torr.

The following carbonic acid esters of formula I are obtained in the manner described in examples 1 to 3.

O-[2-(2',4-dichlorophenoxy)-5- chlorophenyl ]-0-( 2-phenoxy-phenyl) carbonate 0-[2-(2',4'-dichlorophenoxy)-5- chlorophenyl]-0-[2-(4'-chlorophenoxy)-5- bromophenyl] carbonate 0-[2-(2',4'-dichlorophenoxy)-5- chlorophenyl]-0'-[ 2-( 3 '-trifluoromethyl-4 chlorophenoxy)-5-chlorophenyl] carbonate 257260/0.01 Torr 230-240/0.0l Torr 255-26.570.01 Torr The carbonic acid esters of general formula I have an excellent growth-inhibiting action in various series of tests, such as the incorporation test (testing of the growth of bacteria or fungi on culture medium into yvhi gh various concentrations of the active substances have been incorporated) described by X Biihlmann, W.A. Vischer and H. Bruhin [Zbl. Bakt. Abteilung l, Originale, 180, 327-334 (1960)], and the diffusion test (measurement of the breadth of zones of inhibition) described bfi-i Bruhin and X. B iihlmann [Path Microbiol. 26, 108123 (1963)], against gram positive and gram negative bacteria such as Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Salmonella typhi. Bacteriostatic activity in vitro (diffusion test) The test substance is dissolved in a suitable solvent in a concentration of5,000 'y/ccm.

Sterile strips of filter paper (5 X mm, liquid takeup of each strip about 0 1 com) are dipped in the solution of test substance and then hung up to dry. Each strip is then placed in a petri dish (85 mm inner diameter, filled with ccm culture medium) and the dishes, containing uninoculated medium, are placed for 16 hours in an incubation chamber to allow the test substances to penetrate into the media. Only then is a strip 5 tioned above and put into an incubation chamber for 2 ofthe medium inoculated with the bacteria for the test, X 24 hours at 37C. The marginal concentrations inafter which they are bred for 24 hours at 37C. hibiting the growth of the individual strains are shown As result, the size of the zone of inhibition, including in the fo lo ing Table: the width of the filter paper strip, is given in mm.

10 compound Staph. Bac. Sar. urcae Esch. active substance bacteria aureus pumilus 822 Esch. Klebs. Salm. Staph. SG 8196 coli pneu. typhi aureus NCTC NCTC NCTC NCTC chlorophenoxy)-4- bromo-S- 0,0-b|s-[2-(4-chlorocmomphenyn p ylp y i carbonate 30 30 30 carbonate 45 47 45 55 0,0'. i 2. 2',4'. -l dichlorophenoxy)-4- phenoxy-S-chlorophenyl] 2Q bromo-S- carbonate chlorophenyll 45 47 45 55 carbonate 3 3 3 Bacteriostatic activity in vitro (incorporation test) 25 The following tests were made to determine the bac- The active substance to be tested is dissolved in a teriostatic activity in washing liquors containing suitable solvent and, if possible, the solution is further chlorine: diluted with the same solvent. The concentration of the The active substance, previously disso ved in a ratio solutions of active substance is so chosen that, after adof 1:100 in dimethyl formamide, is added in the condition of the culture medium, the desired final concen- 3O entrations given to a washing liquor containing 2.5 tration is attained. With water as solvent, the ratio of g/ of p and to a Washing l q Containing solutionzculture medium should be about 1:10, with an g/ p and 2 com/liter f an queous sodium organic solvent it is generally 1:100. in order to exclude hyp Solution n ng 15 percent active a bacteriostatic action of the solvent used, a control is Chlorine Cotton fabric is introduced into his run with the solvent, liquor (liquor ratio 1:20) and the liquor is heated to Still liquid agar culture is added to the solution of ac- C The e t e i t eated for 20 minutes at this temtive substance and the ixt i poured i t t i perature, then rinsed twice for 3 minutes at C with dishes so that each contains 20 ccm. After it has permunt-Water q ratio wrung out a f solidified, the culture medium is inoculated with suitadiied- CirClilai Samples mm diameter) are out from ble suspensions of-bacteria. The media are then placed 40 this Washed and treated textile and laid on g Plates in an incubation chamber for 24 hours at 37C. The test which have been inoculated previously With 24 hour is evaluated by determining the lowest concentration at Old cultures of Staphylococcus ahi'ehs 511 or which growth ofthe bacteria is completely inhibited. f i coli The agar Plates are P into The figures given in the following Table are the ahihcubahhg Chamber 24 hours at minimal concentration which inhibits growth. They are The Values summarizecl following Table give shown in ppm (parts of active substance per 10 parts the extent ot the zones of inhibition around the sample of diluent), which corresponds to an amount of l 'y per in i the Sign means formation of colonies and com the sign means formation of colonies under the sample.

. active substance bacteria Esch. Klebs, Salm. Staph. coli pneu typhi aureus NCTC NCTC NCTC NCTC f fgg 335:; E Co 86 7242 8384 7447 A B A B 0,0-bis-[2-(4-chlorophenoxy)-S- -p e y) i bromophenyl] carbonate 5O 8- 6- 7- 6- phenyl]carbonate I 1 1 l I 100 0,0'-bis-[2-(2',4'- 200 l2 7- 9 7 P w- 0,0'-bis-[2-(4'chlorophenoxy)4- chlorophenyl] carbromo-S-chlorophenyl] bonate l 1 1 1 carbonate 100 5- l 2- 0- 200 6- 2- 2 l- 0,0'-bis-[2-(2',4-

dichlorophenoxy)-5- The bacteriostatic action of some compounds acbromoplienyilcatbonate 83 gcording to the invention was tested on the following 2T 2 strains of bacteria: Staphylococcus aureus SG 511, dliltihlorqlpheqoxwiwfi- Escherichia c0li8l96, Bacillus pumilus J.R.G. I32, Sarc 0mm 38 g: g: 3: g: cina ureae J.R.G. 822. 200 o 6- 3 3-- The agar incorporation test according to Leonard and Blackford was used as test method. Nutrient agar plates containing 100, 30, 10 and 3 ppm active substance are inoculated with solutions of the strains men- 0,0'-bis-[2-(4'-chlorophenoxy)-5- chlorophenyllcarhonnte 50 8- 6- 7- 5- 100 lO- 7- 7- 6- 200 IO- 8- 8- 9- chlorophunyllcarbonute 50 6- 5 7- 4- IOO 6- 9'- g 0,0'-bis-[2-(4'-bromophenoxy)-5- 20o bromophenyllcarbonste 50 9- 6-- 6- 4- I 9- 8- 6- 200 10-- 8- 7 6- di-[2-(4'-chlorophenoxy)-5- chlorophenylloxalate 50 11- 0+ 10- 0+ 100 11- 0+ l2- 0+ 200 I3- 0+ 12- 0+ di-[2-(2',4'-dichlorophenoxy)-5- chlorophenylloxalate' 50 9- 0+ 8- 0+ 100 10- 0+ 9- 0+ 200 12- 0+ 10- 0+ 2-hydroxy-4,4'-dichlorodiphenyl ether 50 9- 0+ l0- 0+ 100 13- 0+ l3- 0+ 200 14- 0+ 14-- 0+ trichlorodiphenylether 50 IO- 0+ 7- 0+ I00 12- 0+ 9 0+ 200 13- 0+ 9 0+ compounds known from British Pat. No. 1,024,022 and Belgian Patent No. 659,636.

This stability of action of the carbonic acid esters according to the invention is maintained not only in washing liquors containing hypochlorite but also generally in all washing or rinsing liquors which contain active chlorine.

As wash-active substances, washing or rinsing liquors can contain, e.g., anion active compounds such as aromatic sulphonic acids substituted by lipophilic groups or their water soluble salts such as the sodium salt of dodecylbenzene sulphonic acid, or water soluble salts of sulphuric acid monoesters of higher molecular alcohols or their polyglycol ethers, e.g., soluble salts of dodecyl alcohol sulphate, or of dodecyl alcohol polyglycol ether sulphate, or alkali metal salts of higher fatty acids (soaps), also non-ionic wash-active substances such as polyglycol ethers of higher fatty alcohols, also polyglycol ethers of higher molecular alkylated phenols as well as so-called amphotericf washactive substances, e.g., reaction products of the alkali metal salts of low halogen fatty acids with polyalkylene polyamines containing lipophilic radicals such as with lauryl diethylenetriamine. In addition, the liquor can also contain the usual auxiliaries such as water soluble perborates, polyphosphates, carbonates, silicates, optical brighteners, plasticizers, salts having an acid reaction such as ammonium or zinc silicofluoride, or certain organic acids such as oxalic acid, also finishers, e.g., those based on synthetic resins, or starch.

Primarily organic fiber material, chiefly that of natural origin such as that containing cellulose, e.g., cotton, or containing polypeptide, e.g., wool or silk, or fiber material of synthetic origin such as that based on polyamide, polyacrylonitrile or polyester, or mixtures of the fibers mentioned above, can be sterilized with such washing or rinsing liquors containing active substance.

In concentrations of about 1 200 ppm, the carbonic acid esters according to the invention lend both to the liquor as well as to the articles washed therewith substantial and long-lasting freedom from germs of the Staphylococci and Coli forms, and this is maintained even after exposure of the active substance or of the goods treated therewith. They differ from previously known compounds by their stability to light on the goods laundered therewith and by their great activity and breadth of action against gram positive and gram negative micro-organisms.

The new carbonic acid esters are also very effective against bacteria which cause perspiration odours so that they are suitable as deodorants for personal linen and for incorporation in cleaning agents such as soaps or shampoos, or as additives to other cosmetics.

In addition, the carbonic acid diphenyl esters can be incorporated direct into the material to be protected, e.g., into material having a synthetic resin bases such as polyamide and polyvinyl chloride, into paper treatment liquors, into printing thickeners made of starch or cellulose derivatives, into lacquers and paints which contain, e.g., casein, into cellulose, into viscose spinning masses, paper, animal glues or oils, into permanent sizes based on polyvinyl alcohol. In addition they can also be added to preparations of inorganic or organic pigments for the painting and decorating industry, plasticizers, etc.

The carbonic acid esters of formula I can further be used in the form of their organic solutions, e.g., as sprays, in dry cleaning additives, or the impregnation of wood. For this purpose, organic solvents, preferably non-water miscible solvents, particularly petroleum fractions, also however, water miscible solvents such as low alcohols, e.g., methanol or ethanol or ethylene glycol monomethyl or monoethyl ether, can be used. The carbonic acid esters of formula I can be used in the form or their aqueous dispersions together with wetting or dispersing agents, e.g., for the protection of substances which tend to rot, e.g., leather, paper, etc.

Solutions or dispersions of active substance which can be used for the protection of these materials should have a content of active substance of at least 0.001 g/litre.

In all these forms the new carbonic acid esters of general formula I can be the sole active substances or they can be combined with other known antimicrobial, particularly antibacterial and/or antimycotic active substances. They can be combined with, e.g., halogenated and/or halogeno-alkylsubstituted salicylic acid alkylamides and alkyl anilides, halogenated and/or halogenoalkyl-substituted diphenyl ureas, optionally halogenated benzoxazolones, polychlorohydroxydiphenyl methanes, halogen-hydroxy-diphenyl sulphides, halogenated hydroxydiphenyl ethers, bactericidal 2-imino-imidazolidines or bactericidal quaternary compounds, dithiocarbamic acid derivatives or with tetramethyl thiuram disulphide. A broadening of the range of action and/or synergism occurs in some of the combinations mentioned of the carbonic acid esters usable according to the invention with other antimicrobial substances.

EXAMPLE4 To a detergent composition liquefiable at high temperature and composed of 40 parts of sodium soap based on lauric, myristic and palmitic acid,

30 parts of sodium tripolyphosphate,

5 parts of tetrasodium pyrophosphate,

4 parts of sodium silicate,

3 parts of magnesium silicate,

0.5 part of tetrasodium salt of ethylene diamine tetraacetic acid, parts of sodium carbonate, 5.5 parts of sodium sulfate and 70 parts of water, there are added at 85 to 90 0.2 part of l-(3'-chlorophenyl)-3-(4"-chlorophenyl)-pyrazoline (optical brightener), and 1.0 part of 0,0-bis-[2-(2,4-dichlorophenoxy)-5- chlorophenyl] carbonate. The components are thoroughly mixed and then dried in the spray tower. A spreadable bactericidal detergent is obtained.

EXAMPLE 5 200 parts of soap powder, consisting of 88.0 mixture of the sodium salt of tallow fatty acid and sodium salt of coconut oil fatty acid (weight ratio 70:30), 2.0 almond oil, 1.0 perfume, 0.2 titanium dioxide, 0.5 glycerol, 0.05 tetrasodium salt if ethylene diamine tetraacetic acid, 0.05 l-(3'-chlorophenyl)-3-(4"-chlorophenyl)- pyrazole (optical brightener), 2.0 0,0-bis-[2-(4-bromop henoxy)-5-bromophenyl] carbonate, and 6.2 water, together with 400 parts of water are worked at 80 into a homogenous mass and then dried at 70 to 80 in vacuo. A brightened bactericidal soap material is obtained which can be formed into pieces or ground into a powder.

EXAMPLE 6 992 parts of a heavy-duty non-soap synthetic detergent consisting of 152 parts of dodecyl benzene sulfonate,

38 parts of sodium salt of lauryl alcohol sulfonic acid ester,

256 parts of sodium tripolyphosphate,

76 parts of .tetrasodium pyrophosphate,

40 parts of sodium silicate,

19 parts of magnesium silicate,

50 parts of sodium carbonate,

14 parts of carboxymethylcellulose,

0.3 part of tetrasodium salt of ethylene diamine tetra-acetic acid, and

343 parts of sodium sulfate are mixed with 1,000 parts of water to form a homogenous slurry. To this mixture are added 1 part of 4,4-bis-[4",6"-diphenylamino-1 ",3 ",5-triazinyl- (2")-amino]-stil-bene-2,2'-disulfonic acid (optical brightener) and parts of 0,0-bis-[2-(4'- chlorophenoxy)-5-chlorophenyl] carbonate, the whole is mixed well then dried in the spray tower and ground into a powder. A bactericidal synthetic detergent is thus obtained. 1

We claim:

1. A washing agent consisting essentially of (l) a wash-active substance selected from the group consisting of anionic, nonionic and amphoteric detergents and (2) an anti-bacterially effective amount of a bis- (phenoxyphenyl) carbonate of the formula 5 (phenoxyphenyl) each of R R R and R represents hydrogen or halogen of an atomic number of at most 35, and

each of the benzene rings B and B is unsubstituted, monoto tri-substituted by a member selected from the group consisting of halogen of an atomic number of at most 35 and lower alkyl, or monoor di-substituted by trifluoromethyl.

2. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0-bis-[2-(2,4- dichlorophenyl] carbonate.

3. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0-bis-[2-(4'- chlorophenoxy)-5-chlorophenyl] carbonate.

4. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0-bis-[2-(4'- bromophenoxy)-5-chlorophenyl] carbonate.

5. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0'-bis-[2-(4- bromophenoxy)-5-bromophenyl] carbonate.

6. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0-[2-(2',4- dichlorophenoxy)-5-chlorophenyl]-0'-[2-(4- chlorophenoxy)-5-chlorophenyl1 carbonate.

7. A method for the sterilization of laundered goods and for the protection of laundered goods from attack by bacteria, which method comprises treating the goods with a liquor which consists essentially of washactive substance selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of a bis-(phenoxyphenyl) carbonate of the formula wherein each of R R R and R, represents hydrogen or halogen of an atomic number of at most 35, and each of the benzene rings B and B is unsubstituted, monoto tri-substituted by a member selected from the group consisting of halogen of an atomic number of at most 35 and lower alkyl, or monoor di-substituted by trifluoromethyl. 8. A method according to claim 7 in which the biscarbonate is 0,0-bis-[2-(2',4'- dichlorophenoxy)-5-chlorophenyl] carbonate.

ll 12 9. A method according to claim 7 in which the bis- (p yp y carbonate is -l (phenoxyphenyl) carbonate is 0,0-bis-[2-(4'- I bromophenoxy)-5-bromophenyl] carbonate. chlorophenoxy)-5-chlorophenyl] carbonate. 12. A method according to claim 7 in which the bis- ]0. A method according to claim 7 in which the bis- (phenoxyphenyl) carbonate is 0-[2-(2,4- (phenoxyphenyl) carbonate is 0,0'-bis-[2-(4'- 5 diChl0r0phenoxy)-5-chlorophenyl]-0-[2-(4 bromophenoxy)-5-chlorophenyl] carbonate, chlorophenoxy)-5-chlorophenyl] carbonate.

11. A method according to claim 7 in which the bis- V =r a 

1. A washing agent consisting essentially of (1) a wash-active substance selected from the group consisting of anionic, nonionic and amphoteric detergents and (2) an anti-bacterially effective amount of a bis-(phenoxyphenyl) carbonate of the formula
 2. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(2'',4''-dichlorophenyl) carbonate.
 3. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-chlorophenoxy)-5-chlorophenyl) carbonate.
 4. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-bromophenoxy)-5-chlorophenyl) carbonate.
 5. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-bromophenoxy)-5-bromophenyl) carbonate.
 6. A washing agent according to claim 1 in which the bis-(phenoxyphenyl) carbonate is 0-(2-(2'',4''-dichlorophenoxy)-5-chlorophenyl)-0''-(2-(4-chlorophenoxy)-5 -chlorophenyl) carbonate.
 7. A method for the sterilization of laundered goods and for the protection of laundered goods from attack by bacteria, which method comprises treating the goods with a liquor which consists essentially of wash-active substance selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of a bis-(phenoxyphenyl) carbonate of the formula
 8. A method according to claim 7 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(2'',4''-dichlorophenoxy)-5-chlorophenyl) carbonate.
 9. A method according to claim 7 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-chlorophenoxy)-5-chlorophenyl) carbonate.
 10. A method according to claim 7 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-bromophenoxy)-5-chlorophenyl) carbonate.
 11. A method according to claim 7 in which the bis-(phenoxyphenyl) carbonate is 0,0''-bis-(2-(4''-bromophenoxy)-5-bromophenyl) carbonate. 